Dehydrogenation of hydrocarbon oil and catalyst therefor



Patented Sept. 13,1949

nnmmno "amnion F HYDROCARBON on. n CATALYST THEREFOR William H. Claussen and Homer B. Wellman,

Berkeley, Calif., assignors. by mesne assign- -ments, to California Research Corporation, San

" I z,481.szi

Francisco, Calif., a corporation of Delaware No Drawing. Application October 4, 1944, Serial No. 557,236

2 Claims. (Cl. 196-78) 1 This invention pertains to the catalytic treatment of hydrocarbon distillates, and more particularly to the composition and method of preparation of a particular type of solid catalyst tivity and highest durability may be realized. It is afurther object of our invention to provide a molybdenum-aluminum compound material of great catalytic activity and long active life which is at the same time of sufilcient purityand in such physical form as to be capable of compression into catalyst forms that are suited to pracwhich has been found especially useful in the 5 tical use and have suflicient resistance to crushantiknock improvement of gasolines and in the ing and to abrasion to withstand the usual hazconversion of low boiling petroleum fractions to ards of. industrial service throughout the cataaromatics. lytically active life of the component materials.

This application is a continuation-in-part of In preparing the coprecipitated molybdenumour application Serial No. 446,528, filed June 10, containing catalysts of the present invention, we 1942, and now abandoned. have found that the characteristics of the salts The use of molybdenum-containing catalysts, from which molybdenum and aluminum composuch as molybdenum oxide supported on active nents are derived, the concentration of the solucharcoal, activated silica or activated alumina, tions from which the coprecipitate is deposited, has been proposed for effecting various hydrothe conditions of precipitation, the method of carbon reactions. While the best such catalysts collecting and purifying the precipitate, and the may be satisfactorily active when first prepared, procedure employed in washing, drying, grinding, they rapidly lose activity on repeated regenerapelleting and calcining the precipitated material tion and they are also frequently unable to withare all significant to the preparation of the most stand even the minimum of handling and atactive and the longest-lived catalysts. It has furtendant abrasion which is necessary in the usual ther been found that in order to realize the greatcommercial operation of a heterogeneous cataest activity and the longest catalyst life, the forelytic process. We have now found that if, ingoing variables must be so correlated as to protead o positing the mo y de u pon n duce afinished catalyst consisting essentially of On the su face a d in the Pores a e t a solid solution of molybdic oxide in gamma aluiS co b ed 0 p pitated with the other inmina containing relative larger pore spaces and redients which it is desired to include in the a crystal lattice constant of somewhat greater dia ys Composition, a c y t vin ed mensions than is found in the catalysts of more upe in activity. in l t of active e and or less similar empirical composition that have n its a y to withstand crushing and abrasion hitherto been disclosed for similar uses and prec'an be produced. For instance, when a molybdepared by depositing and supporting the molybdic mun c pon s P pitated together wit an oxide on-preformed and activated alumina. aluminum component f om an aqu us s t n As a source of the aluminum component we containing soluble compounds of these two elehave found t t aluminum chloride, ember ments and the re i p cipitate is thoroughl hydrous or hydrated, aluminum acetate or aluwashed. car u y dri d d perly heat tr at d. minum nitrate may be used with about equal a compound ca s is p d which has very results. Taking aluminum chloride as typical, superior p pe when employed win the ewe have found that a solution containing about forming of gasoline for the antiknock improve- 10 by weight or approximately 0.52 pound ment thereof, and particularly in the production 40 per gallon is particularly suited t our purpose of substant lly p r aromatic liquids from low though solutions containing from about 0.05 to o n Petroleum distillatesabout 2.5 pounds per gallon may be found suited It is accord n y an Object of s invention to to certain special conditions. It has been found provide an improved process for the treatment that the molybdenum component of t of low boiling hydrocarbons with an improved cipitated catalyst may be supplied fro a solutype of molybdenum-containing catalyst wherein man of ammoniummolybdate, (NI-102M004; a compound that element is combinefl and monium dimolybdate, (NH4)2MozO'1; or ammoniprecipitated with a compound of aluminum and um heptamolybdate, (NHOGMMOM' as may be the resulting pricipitage is g g i f most convenient. If these ammonium salts are duce a more act ve an more ura e ca a ys or use in heterogeneous hydrocarbon reactions than 11,01: vallable a such entlrely satisfactory soul has heretofore been available from these elenon for use m preparmg our preferred catalysts may be easily had by dissolving either molybdic ments. It is also an object to provide a method of producing this molybdenum-aluminum cataacid 9 molybdlc anhydrid? the appropriate iyst whereby the combinations of greatest'acquantlly of aqueous ammomawhen the hepta" molybdate is employed it has been found to give.

most satisfactory results at about 1.6 pounds per gallon of solution, though solutions ranging l 3 from about 0.2 to 8.0 pounds per gallon may someaqueous ammonia until precipitation is complete.

everse order of addition may also be em- 3351. Another satisfactory procedure is to first mix the ammonia and the molybdenum salt solutions and then to add this mixture to the aluminum chloride solution or to add the aluminum chloride solution to the mixture. When employing the solutions above described at the preferred concentrations there given, it has been found that an ammonia solution containing about to NH: is particularly suited to effect the precipitation, though it will be appreciated that with other strengths of salt solutions either weaker or stronger ammonia solution may be f rabl it has been found that markedly superior results are obtained when the precipitation is approached from the acid side with respect to the aluminum component, as will be the case when the precipitation is from a solution of an aluminum salt of an intermediate or strong acid such as aluminum chloride. It has been found that when the aluminum chloride solution or its mixture with the ammonium molybdate solution has an initial pH of about 4.0 or below and the ammonia containing solution is added slowly with vigorous agitation until a pH of about 8.0 is reached, the most activedand most durable catst material is produce lqot only is the approach to precipitation of the alumina from the acid side, as just described, a significant feature of the present invention but we have also determined that the substantial absence of any alkali metal component, and particularly of a sodium component, from the molybdenum-aluminum coprecipitate is essential in order that the catalysts made therefrom may have maximum activity and maximum life. It has, for instance, been found that 0.6% of sodium oxide included in a molybde num-aluminum coprecipitate will reduce its activity to about 60% of that of a catalyst containing no alkaline oxide. It is thus necessary for best results to keep the sodium content, expressed as metal, below about 0.1% and preferably below 0.05% by weight of the catalyst.

While this desired low sodium content may possibly be secured when precipitation is from an alkaline solution, such as the customary solution of sodium aluminate, if resort is had to long and thorough washing of the precipitate, such procedure is not only troublesome, time consuming and expensive but inefficient in that substantial quantities of the molybdenum component will also be washed away. Precipitation from an acid solution of the appropriate salts, utilizing ammonia as the sole alkaline reagent as already described, thus not only results in a more rapid and more convenient but also in a more economical process and a more active catalyst than has hitherto been described.

The precipitate, thus carefully prepared, and especially when the less concentrated solutions of the reacting salts are used, is a thoroughly homogeneous fiocculent mass or weak gel which X-ray studies of the washed and calcined precipitate indicates the material to consist of a uniform solid solution of molybdenum 'oxide'in an excess of gamma alumina. No molybdic oxide as such is to be found in the product. This fact is believed to be one of the fundamental reasons for the desirable characteristics of our preparation. In any event the coprecipitate from an acid solution, as further brought out hereinafter, yields on proper handling a catalyst which is far superior to the best hitherto disclosed molybdenum catalysts consisting of molybdenum oxide supported on an appropriate carrier. It will thus be understood that when we herein refer to is readily broken up and collected for further Y processing. The best evidence available from the catalysts of this invention as copreclpitated" molybdenum-aluminum compositions, the term is intended to comprehend the material produced according to the method specifically set forth or its reasonable equivalent irrespective of whether it is merely a mixture of separate compounds of the two elements, a solution of the one oxide in the other or whether a definite compound can be shown to exist between them.-

At least a suggestion of compound formation is to be found in the fact that in the preferred range of precipitation wherein the atomic ratio of aluminum to molybdenum in the precipitating solutions is betweenabout l5 and 25 to 1, moderate variations in the proportions of molybdenum and aluminum result in precipitates which, when washed substantially free of soluble salts, contain a more nearly constant quantity of molybdenum than would ordinarily be expected. This apparent transitory or pseudo equilibrium composition contains between about 6 and 8% by weight of molybdenum, expressed as the element. It has been found that material of this composition is particularly well adapted to the preparation of catalysts for the production of aromatics.

After precipitation is complete at a pH of about 8.0, it has been found that subsequent handling is very much facilitated if the suspension is permitted to stand for a period of several hours in order to permit the finer particles to coagulate. The solid may then be readily collected by either filtration or decantation methods as usually employed. When 'decantation is used, from two to as many as five or six washings may be necessary in order that the ammonium chloride content of the finally dried product will be sumciently lowto give the most serviceable material. The same result may be effected by filtration separation if the filter cake is redispersed in pure water and recollected several.

times. Whichever method is employed, the washing should be continued to such an extent that the product when substantially dried will invariably contain less than 10% of ammonium chloride in order that the product may be compressed into catalyst shapes that retain a high proportion of their mechanical strength after the degree of heat treatment that is necessary to bring the catalyst to its condition of maximum activity,

In a typical instance, starting from aluminum chloride and ammoniumheptamolybdate solutions the first filter cake was found to contain 87% water, 6% ammonium chloride, and 7% of the desired coprecipitate. On being dispersed in fresh water and refiltered, the cake contained about 90% water, 2% ammonium chloride, and 8% coprecipitate, and on second redispersion and collection contained 92% water, 0.6% ammonium chloride, and 7.4% coprecipitate. On a 8 water free basis this last product will be seen to contain but 7.5%! ammonium chloride.

The finally washed filter cake should be broken up and dried until it contains no more than about 30% water. This preliminary drying step can be accomplished at anysuitable temperature between about 100 and about 850 F. or above. The thus dried material is a white solid which, in contrast to some of the hard glassy gels previously disclosed may be ground to an easily pelleted powder. It will preferably contain about 74% of the moylbdenum-aluminum coprecipitate and about 6% or less of ammonium chloride.

The total content of components in this preliminarily dried product that are volatilized on calcining is extremely significant to the next succeeding step of pelleting and should always be between about 20 and 30% and preferably between 24 and 28% in order to give pellets of the 20 maximum strength for a given pressure applied in their preparation.

The catalyst dried to a water content of about 20% is ground to produce a powder having more or less the following mesh analysis:

- Per cent Through 50 mesh 100 Through 100 mesh 75 Through 200 mesh 34 If ground substantially finer than this the pellets subsequently produced are unsatisfactory because of splitting, while coarser material is not so easily handled in the step of pellet preparation. If, however, a lubricant is added to the powder before pelleting, some additional leeway may be possible in the suitable range of powder dimensions. It has been found that a few per cent (usually between 1 and of powdered graphite, of stearic acid, of bentonite, of rosin or of a /saturated high boiling hydrocarbon oil, will serve as a satisfactory lubricant, the exact material and quantity depending somewhat on the composition of the catalyst and the specific service in which it is to be used.

The dried powder containing the desired lubri-' cant is next compressed into pellets of any desired shape, as for instance cylinders, spheres or various rectilinear shapes by means of any suitable tablet or pill machine. Pellets varying from about 0.1 to 0.75 inch in their longest dimension have been found well suited for use in the hydrocarbon reactions contemplated. The pressure employed to produce the pellets should be sufficient to give good mechanical strength but not enough to produce such dense particles that their catalytic activity is materially reduced. For instance, cylindrical particles having rounded ends and a diameter of 0.187 inch have been prepared with a crushing strength well above 40 pounds'as measured by subjecting them to a uniformly increasing pressure applied through a steel plunger having a diameter of 0.02 inch. However, it has been found that at higher com pressions some loss in activity may be expected. Strengths from about 6 to 25 pounds have been found quite satisfactory, with about 12 to pounds being the preferred figure for catalyst particles of the foregoing range of sizes.

The arbitrary unit of "crushing strength just referred to is more convenient to measure and use for comparative purposes than the customary v more cumbersome figure for compression strength as measured on a special sample between flat plates. The relation between the crushing strength of the catalysts of our invention as employed here and their compression strength is substantially linear and of the 15 The catalyst pellets must be subjected to a final calcining step before they are ready for use in order to remove the residual ammonium chloride and water. The temperature of calcining may be conveniently at about 1100 F. or above, and we have found a preferable procedure to be a slow heating of approximately three hours' to reach this temperature, followed by at least two hours of constant temperature at that point. This removes ammonium chloride and water but, of course, not the graphite added, as pointed out above, which inherently and necessarily under these conditions remains present in the finished catalyst, producing a catalyst having superior properties, particularly one having a higher activity for a longer period of time, that is, a longer life. While various other procedures for calcining may be employed as conditions dictate, it has been found that the minimum satisfactory calcination requires at least three hours at 800 F. and the maximum may be for as long as 150 hours or more at temperatures as high as 1300 F.

As pointed out above, the finished catalyst containing graphite is superior in that it has a higher activity fora longer period of time. Evidence W indicates that this may be due to a reducing effect of the graphite present in the catalyst while in use. It appears that during regeneration, when the carbonaceous deposit is burned from the catalyst with an oxygen-containing gas, the

graphite has the efiect of lowering the tendency 'of the metallic component, suchas molybdenum,

to be oxidized to a higher state of oxidation. which higher state of oxidation has a disadvantageous effect upon the catalyst.

Graphite may also be used in the finished catalyst material where, instead of the molybdenum component as described above, other metallic components may be used, preferably in the oxide form as with the molybdenum component, including metals of groups V and VI,

particularly vanadium, chromium and tungsten.

Moreover, graphite will be found advantageous in the catalyst material where there is present a component susceptible to an undesirably high stage of oxidation when subjected to the oxygencontaining gas for regeneration with a resultant lowering of the effectiveness of the catalyst or its life. This feature is of great importance, particularly for catalysts which are used in a cyclic process involving on-strearn and regeneration periods where the regeneration is effected with an oxidizing agent such as air usually with a controlled oxygen content. Instead of the aluminum component as described above, other components such as silica, beryllia, zinc oxide, etc., may be ,used in the combination with graphite.

Moreover, advantages of graphite may be obtained when the catalyst material is made by other methods such as by impregnating an activated alumina or an alumina gel with the other metallic following magnicomponents as with molybdenum oxide, for exam le.

This ability of the catalysts of our present invention to withstand long periods heating at high temperatures and in fact to gain in catalyst activity by reason of suchv treatment, with sub- 'stantially no loss in mechanical strength, is one of their points of outstanding superiority over other known catalysts in this fleld. We have in fact adopted a standard accelerated lifetest that all of our catalysts must pass before being considered suitable for commercial use. This test requires that the catalyst show the same or increased activity after being held for one week (168 hours) at 1300 F. as it had before heating. Catalysts of the impregnated type wherein molyb-.

denum oxide is supported on activated alumina are substantially sintered and lose practically all of their catalytic activity when subjected to such treatment.

The large immediate practical advantage derived from this ability of our catalysts to withstand high temperatures is, of course, in connection with the regeneration treatment for removal of carbon which collects on the catalyst during use. With former catalysts of the supported type the temperature of reburning had to be rigorously lrept below above 1200 F. in order to prevent serious loss in activity of the catalyst. In order to realize this end, elaborate precautions had to be taken and provision made to carry away the heat of the reaction. By contrast the thermally more rugged catalysts of our invention require much less careful temperature control during the reburning operation'and thus permit a substantial increase in the speed of this opera tion.

Instead of proceeding by way of the precipitation and washing steps previously described, it may sometimes be found desirable to effect the precipitation from substantially more concentrated solutions than those indicated as preferable and then to subject the whole mass, without any attempt at filtration, to the preliminary drying step, after which the ammonium chloride and other impurities may be eliminated by ex-' traction or other suitable methods of leaching. While the filtration step and the apparatus necessary therefor may thus be eliminated, the saving in apparatus is at least in part offset by the additional drying step required.

An idea of the superiority of the coprecipitated catalysts of the present invention over the best previously known molybdic oxide on activated alumina catalysts may be had from the data presented in the following table which were obtained in reforming the same charging stock under wholly comparable conditions:

8 It will be noted that not only were the fresh coprecipitated catalysts from 25% to more active than the best supported catalyst but thev activity actually increased in-the accelerated life test (168 hours 1300 F.) by several per cent while that of a supported catalyst decreased by about 92%. I

Some further understanding of the nature of the catalysts of the present invention and their relation to the supported-molybdic oxide catalysts of the prior art may be had from the following X-ray and adsorption data;

Comparison of catalysts coprecipitated Surface area s meters per gram:

Fresh cimhyst (Granular) Fresh Catalyst, pelleted... 168 1300" F as a While the substantially complete loss of catalytic activity by the supported catalysts is consistent with and apparently attendant upon the almost complete collapse of the catalyst pore structure, the ultimate cause of this condition is probably to be found in a more fundamental condition which is revealed only by an X-ray analysis. The lattice constant for gamma alumina in terms of our present apparatus is 7.86 A. This willbe seen to beexactly the same as that for the supported molybdic oxide catalysts both before and after heat treatment. It is therefore apparent that the association of the molybdic oxide with the'alumina is not sumciently deep seated to alter the fundamental structural arrangement of the alumina molecules. The relationship is thus only superficial and the catalytic efiect might well be expected to be more or less fugitive. On the contrary, the molybdenum compound in the coprecipitated catalysts is so tied into the fundamental arrangement of molecules as to cause a small but real alteration in the dimensions of the ultimate crystal unit. Whatever the catalytic efiect of such a change, it would certainly be expected to be an enduring effect.

As a further example of the remarkable utility of the catalysts of this invention, a pelleted, co-

Heat treatment. of catalysts catalyst Treatment fgfggi M00; on Grade A Activated Alumina (prepared HeatedShours at 900 F.inair 60 v by impregnation).

same Heated 164 hours at 1200 F. in air.-.-.

same samelanotber similar preparation). same Granular coprecipitated Moiybdenum-Alumina same Heated 331 hours at 1200" F. in air Heated 5 hours at 900 F. in ai Heated 168 hours at 1300 F. in air Fresh, heated 2 hours at 1100 F. in air. Heated 168 hours at 1200 F. in air. Heated 335 h mm at 1200" F. in air.

same {another preparation) Fresh, heated. 2 hours at 00 F. in a same another preparation)" Fresh, heated: 2 hours at 1100 F. in air.

same, pelleted toys" pills... Fresh. heated 2 hours at 1100 F. in air..-;--..

same, pelleted to 9i." pills--. Heated 168 hours at l300 F. in air 107 1 Relative aotivi is portlonal to the ieed rate re uired to obtain a ven conversion of l-Zi0 F. ti item Kettlsman aide go q a m on aromatics under a given set oi conditions.

precipitated molybdenumaluminum catalyst, prepared according to the foregoing procedure and containing 9.2% molybdenum (calculated as metal) was employed in the first catalyst stage of a two-stage process for the production of toluene from a selected fraction of California petroleum. In this operation a distillate boiling between about 180 and 230 F. was passed over the catalyst at a temperature of about 955 F. under a Pressure of 115 p. s. i. at a charging rate of about one volume of liquid per volume of catalyst per hour and in the presence of a carrier as containing about three molecules of hydrogen per molecule of the hydrocarbon charge. A cut boiling between 227 and 232 F. amounting to 20.5% of the charge and having an aniline point of 4-78? F. was recovered from the liquid reaction product.

While the utility of our novel coprecipitated molybdenum-aluminum catalyst materials has been illustrated with reference to the dehydrogenation and aromatization of a petroleum discatalytic component comprising molybdenum oxide, for a periodof time sumcient to deposit carbon on said catalyst whereby its activity is lowered and regeneration thereof made necessary, regenerating said catalyst by contacting with an oxygen-containing gas at an elevated tempera ture to remove said carbon deposits by combustillate for the produotionof toluene, they are also highly active in the reforming and desulfurization of naphtha stocks, in the dehydrogenation of cyclic hydroxy compounds such as cyclohexanol, in the cyclization of straight chain compounds such as heptaneand in ring closure and dehydrogenation, such as in the conversion of butyl benzene to naphthalene. They are also useful in the dehydrogenation of ethyl benzene to styrene and of butane and butane to butadiene.

Having now described and exemplified a new group of catalysts comprising coprecipitated molybdenum and aluminum components having superior activity and long life in dehydrogenation, reforming, cyclization and related reactions and having fully describedpractical methods of preparing these coprecipitated catalysts, we claim:

1. In the process of producing dehydrogena-- tion catalyst pellets from a catalytic material between about 1 to 10% by weight with the catalyst material prior to pelleting, calcining the resulting pellets by heating for about 3 hours to tion, during which operation said graphite functions to prevent said molybdenum oxide from attaining an undesirably high degree of oxidation.

WILLIAM H. CLAUSSEN. HOMER B. WELLMAN.

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